CN102443231B - Manufacturing method of PVDC film with crystal point eliminated and barrier property improved - Google Patents
Manufacturing method of PVDC film with crystal point eliminated and barrier property improved Download PDFInfo
- Publication number
- CN102443231B CN102443231B CN201110347831.2A CN201110347831A CN102443231B CN 102443231 B CN102443231 B CN 102443231B CN 201110347831 A CN201110347831 A CN 201110347831A CN 102443231 B CN102443231 B CN 102443231B
- Authority
- CN
- China
- Prior art keywords
- pvdc
- traction
- film
- resin
- stretch ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92923—Calibration, after-treatment or cooling zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a manufacturing method of PVDC film with crystal point eliminated and barrier property improved. According to the invention, an auxiliary agent with a certain proportion is added to a PVDC copolymer; also, a small amount of a thermal stabilizing agent, a lubricant and an inorganic oxide are added to the PVDC copolymer. The formulation of the auxiliary agent is first carried out, and the auxiliary agent and the PVDC resin are blended according to a certain ratio and a certain sequence. The mixture is subject to a blow molding technology by using a single-screw extruder, such that the film is obtained by blowing. According to the invention, a novel plasticizing agent is adopted, and a proportion is optimized, such that a total auxiliary agent addition amount can be reduced. The prepared PVDC film has a flat and smooth surface; and crystal points with sizes lager than 40 micrometers can be eliminated. The film is advantaged in high mechanical strength, and high steam and oxygen barrier properties. The film can be used in the filed of foodstuff packaging or medicine packaging.
Description
Technical field
The invention belongs to field of packaging material, be specifically related to a kind of manufacture method of eliminating brilliant point, improving PVDC (polyvinylidene chloride) film of barrier.
Technical background
Polyvinylidene chloride (PVDC) is vinylidene chloride (VDC) and the binary of other monomers or the general name of terpolymer, its monomer that copolymerization occurs mainly contains vinylchlorid, vinyl cyanide, vinylformic acid and methyl acrylic ester etc., the content of general vinylidene chloride units is more than 70%.Because the symmetry of PVDC polymer chain structure is high, regularity is high, degree of crystallinity is high, polarity is strong, and internal cohesive energy is high, and spread coefficient is smaller, therefore be to there is at present best water vapour and the polymkeric substance of oxygen-barrier property by the prepared film of PVDC, its barrier property is poly 1500 times, polyacrylic 1000 times, and 100 times of polyester.Be widely used in the packaging fields such as food, medicine, ordnance, wherein purposes is the widest, consumption maximum or in casing film and preservative film field.In addition also to have physical strength high for PVDC film, and toughness is large, organic solvent-resistant and grease, and thermal contraction performance and autohension are good, difficult to burn, the features such as stable chemical nature, meet the requirement of food product pack nontoxicity completely.Guarantor's perfume (or spice) of PVDC casing film, quality guaranteed period reach half a year, and the quality guaranteed period of nylon 11,12 casing films is only 15 days, and the quality guaranteed period of cellulose acetate casing film is only 7 days, and therefore PVDC is a kind of excellent performance, the high-quality packaging material for food of long quality-guarantee period.Can produce in the world at present the following several companies of mainly containing of PVDC resin: Dow Chemical company (60,000 tons/year), Wu Yu company of Japan (20,000 tons/year), ICI company of Britain (20,000 tons/year), Asahi Kasei Corporation of Japan (1.5 ten thousand tons/year), Belgian S Su Wei company (10,000 tons/year).Domestic PVDC resin is mainly developed by Juhua Group Co., approximately 10,000 tons/year of annual production, and molecular-weight average, 7～150,000, is applicable to extruding processing, can on the forcing machine of Canadian MACRO, Japanese Wu Yu company, carry out machine-shaping.
Still there are many problems in the standby film of PVDC resin at present, is mainly manifested in: face unfairness, and brilliant point (flake) is on the high side, poor tensile strength, easily breaks bubble, frangible pouch in bowel lavage process in blown film process, die head needs often to clean, and causes a large amount of material wastes.So-called brilliant point refers to that part particle is large, molecular weight is higher PVDC resin is because its degree of crystallinity is higher, in the screw rod course of processing, inabundant fusion plastification causes, can not mutually disperse equably with PVDC molecular chain around, in blown film process, solidify prior to PVDC molecular chain around, form arrow shaped or spherical zero pour, be called as brilliant point.The feature of brilliant point is in the time improving processing temperature or extend fusion time, can continue fusion plastification; Flake refers to the comprehensive of brilliant point and the impure point that can not plastify completely, impure point can be the organic and inorganic impurity of residual non-PVDC in material or on screw rod, or the cross-linking products of PVDC, or PVDC is owing to being subject to the carbonization point of heat or shearing action formation, therefore reacts the shape that has any similar flake on face in the middle of there will be.Continue to improve processing temperature or extend fusion time can not reduce the formation of flake.Eliminate the way of brilliant point and flake: need to select suitable auxiliary agent, and optimization processing technology parameter is as cleaned screw rod, screw rod processing temperature, extruded velocity, cooling temperature and time, two-way stretch is compared etc., improves the fusion plastification of PVDC, reduces the formation of brilliant point and flake.
PVDC is the polymkeric substance that degree of crystallinity is higher, and process window is narrow, is heated and easily degrades with shearing action, and work in-process usual auxiliaries mainly contains following several: softening agent, and its Main Function is to reduce Intermolecular Forces, improves the processability of resin; Stablizer, is mainly some oxygenatedchemicalss, can stop or delay PVDC film decomposes; Lubricant, reduces the phase mutual friction producing because of mechanical shear stress between PVDC resin and extruder barrel, screw rod when Main Function is film forming, reduce the PVDC material of stagnating in screw rod and die head, effectively prevents thermolysis, also can improve the glossiness of film surface; Inorganic filler, the barrier property of adjustable film, and improve the mechanical property of processing characteristics and film.
The patent (CN1215739) of existing Japanese Asahi Kasei Corporation discloses a kind of method that compound PVDC multipolymer that comprises two kinds of different molecular-weight average is prepared PVDC unitary film, the PVDC copolymer A that wherein molecular weight is higher, weight-average molecular weight is not less than 50000 but be not more than 300000, mainly plays the effect of giving film strength and radiowelding; The PVDC multipolymer B that wherein molecular weight is lower, weight-average molecular weight is not less than 5000 but be not more than smaller in 0.8 times or 80000 of weight-average molecular weight of copolymer A, mainly plays plastification.In method, do not add other liquid plasticizers or substantially do not add other liquid plasticizers.But on water vapor transmission rate (WVTR) and oxygen percent of pass, the barrier property of this unitary film can not be satisfactory, the plasticization effect of the multipolymer B of low-molecular-weight copolymer A to high molecular is limited, still has brilliant put many and problem pockety.Kureha Kagaku Kogyo K.K. discloses a kind of resin combination that contains metachloroethylene copolymer and extrusion processing film-forming method (CN1183111A) thereof.To be the mixing permalon (A) that is made up of at least 2 kinds of metachloroethylene copolymers of 100 mass parts be selected from multipolymer (B2) and the methyl methacrylate of ethylene and vinyl acetate copolymer (B1, EVA), ethene and vinylformic acid, methacrylic acid or its alkyl ester with at least a kind of 0.1～20 mass parts to this resin combination, divinyl, the resin combination that contains metachloroethylene copolymer of multipolymer (B) composition of cinnamic terpolymer MBS resin (B3).This invention has adopted at least two or more polymkeric substance, prepares unitary film by extrusion molding, oxygen-barrier property is not high, and owing to having added the polymkeric substance containing carbonyl such as EVA, has stronger water-absorbent, must decline to the barrier of water vapour.United States Patent (USP) (US4, 686, 148) a kind of metachloroethylene copolymer and film-forming method are disclosed, mainly in the multipolymer of vinylidene chloride, add a small amount of glycerine (as being less than 2% massfraction) to reduce the consumption of other additives, and attempt improves thermostability and the oxygen-barrier property of vinylidene chloride polymer, but not report of the brilliant point of water vapour barrier and face, adding owing to not forming homogeneous mixture system with metachloroethylene copolymer of glycerine, in blending resin, independently exist as second-phase component, therefore this film is in the time contacting with oils food, glycerine is easily extracted out, cause film that fuel-displaced phenomenon occurs.
Summary of the invention
The object of this invention is to provide and a kind ofly eliminate brilliant point, improve the PVDC(polyvinylidene chloride of barrier) manufacture method of film.
The inventive method, by add a certain proportion of auxiliary agent in the multipolymer of PVDC, adds a small amount of thermo-stabilizer, lubricant and inorganic nanometer oxide simultaneously.First carry out the composite of auxiliary agent, then auxiliary agent and PVDC resin are carried out to blend according to certain ratio, order, finally pass through blow molding process by single screw extrusion machine, blowing film forming.Both the brilliant point that PVDC film is large can be eliminated, and high oxygen, water vapour barrier and mechanical property can be ensured again simultaneously.
The concrete steps of the inventive method are:
Step (1). be the softening agent of 1.0～6.0 parts, the thermo-stabilizer of 0.1～3.0 part, the lubricant of 0.1～1.0 part, the inorganic oxide of 0.05～0.5 part by parts by weight, mechanical stirring 1～24 hour at 35～50 DEG C, the auxiliary agent that obtains mixing;
Described softening agent is cyclohexane dicarboxylic acid diisononyl esters (Dinch), epoxy resin ON828, di(2-ethylhexyl)phosphate phenyl octyl group ester, dipropylene glycol dibenzoate, poly-(1,3 butyleneglycol/1,2 propylene glycol) one or any several mixture in adipic acid ester, Trichloroethyl Phosphate, two (2-ethyl, hexyl) different titanic acid ester, dibutyl maleate, Uniflex DBS, dioctyl sebacate, Octyl adipate, tributyl citrate, Tributyl O-acetylcitrate;
Described thermo-stabilizer is the one or any several mixture in antimony thiolate, Bis(lauroyloxy)dioctyltin, hydrotalcite, epoxy soybean oil, epoxy oleum lini;
Described lubricant is the one or any several mixture in stearate, calcium stearate, sodium stearate, Magnesium Stearate, Zinic stearas;
Described inorganic oxide is the one or any several mixture in talcum powder, calcium carbonate, titanium oxide, silicon oxide, polynite, kaolin.
Step (2). PVDC (polyvinylidene chloride) resin is joined in ribbon stirrer, open mixing machine, and at the uniform velocity heat up; In the time that temperature rises to 40～60 DEG C, auxiliary agent is joined in ribbon stirrer, the weight that adds auxiliary agent is 1.0～10.0% of PVDC weight resin, preferably 2～6%; Continue to stir and be warming up to after 70～90 DEG C, start at the uniform velocity cooling, be cooled to 40～60 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 20～30 DEG C slaking 5～10 days, obtains the modification PVDC resin of slaking, to improve the blowing effect of film.
The weight-average molecular weight of described PVDC resin is 10～180,000, for one of them multipolymer of vinylidene chloride and vinylchlorid, vinyl cyanide, methyl methacrylate, methyl acrylate, butyl methacrylate, fumaric acid, maleic anhydride, glycidyl methacrylate, methacrylic acid macrogol ester, wherein the mass content of vinylidene chloride segment in PVDC resin is 75～95%; As preferably, the weight-average molecular weight of PVDC resin is 11～150,000, is one of them multipolymer of vinylidene chloride and vinylchlorid, vinyl cyanide, methyl methacrylate, and the mass content of vinylidene chloride segment in PVDC resin is 80～90%;
Heat-up rate is 0.5～1.5 DEG C/min, and cooling rate is 1～3 DEG C/min.
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 120～130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 155～165 DEG C, 2nd district, 150～164 DEG C, 3rd district, 155～160 DEG C of flanges, 150～160 DEG C of transmodulators, 150～160 DEG C of die bodys, 155～165 DEG C, die head lip, 20～50 revs/min of single screw speeds, 2～8 DEG C of pipe cooling temperatures, 10～20 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 0.8～1.2; Second stage traction is inflation traction, and axial stretch ratio is 2.5～4.0, and stretch ratio is radially 2.0～5.0; Third stage traction is axial tension, and stretch ratio is 1.0～1.3; Fourth stage traction is axial tension, and stretch ratio is 1.1～1.4.
The inventive method adopts novel softening agent and optimizes proportioning, can reduce total additive dosage, the PVDC film of preparation thus, and face is smooth smooth, can eliminate the brilliant point that size is greater than 40 microns; The thickness of PVDC film is at 30 to 50 microns; Film has higher physical strength, and longitudinal tensile strength is greater than 80MPa, and longitudinal fracture elongation is greater than 100%, and transverse tensile strength is greater than 100MPa, and transverse breakage elongation is greater than 60%; Higher water vapour and oxygen-barrier property, steam penetrating capacity be less than 4 grams/(square metre 24 hours), oxygen transit dose be less than 22 cubic centimetres/(square metre 24 hours 0.1MPa), can be used for food product pack or drug packaging field.
Embodiment
Embodiment 1:
Step (1). by the stearate of the antimony thiolate of the cyclohexane dicarboxylic acid diisononyl esters of 1kg, 0.2kg, 0.2kg, the talcum powder of 0.1kg, mechanical stirring 15 hours at 40 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and vinylchlorid of 30kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 75%, weight-average molecular weight is 100,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.0 DEG C/min; In the time that temperature rises to 50 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 80 DEG C, at the uniform velocity lower the temperature with the speed of 2 DEG C/min, be cooled to 50 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 30 DEG C slaking 5 days, obtains the modification PVDC resin of slaking;
Step (3). pass through Micro-45(ME-175-20-ZO) single screw extrusion machine carries out blowing to the modification PVDC resin of slaking, obtains pipe; Concrete technology parameter in blown film process is: 120 DEG C, single screw extrusion machine processing interval Zhong Yi district, 155 DEG C, 2nd district, 150 DEG C, 3rd district, 155 DEG C of flanges, 150 DEG C of transmodulators, 150 DEG C of die bodys, 155 DEG C, die head lip, 20 revs/min of single screw speeds, 2 DEG C of pipe cooling temperatures, 10 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 1.0; Second stage traction is inflation traction, and axial stretch ratio is 2.5, and stretch ratio is radially 3.0; Third stage traction is axial tension, and stretch ratio is 1.2; Fourth stage traction is axial tension, and stretch ratio is 1.2.
Embodiment 2:
Step (1). by the calcium stearate of the Bis(lauroyloxy)dioctyltin of epoxy resin ON828, the 0.2kg of 2kg, 0.4kg, the titanium oxide of 0.2kg, mechanical stirring 24 hours at 35 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and vinyl cyanide of 30kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 80%, weight-average molecular weight is 110,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 0.5 DEG C/min; In the time that temperature rises to 40 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 70 DEG C, at the uniform velocity lower the temperature with the speed of 1 DEG C/min, be cooled to 40 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 20 DEG C slaking 10 days, obtains the modification PVDC resin of slaking;
Step (3). pass through Micro-45(ME-175-20-ZO) single screw extrusion machine carries out blowing to the modification PVDC resin of slaking, obtains pipe; Concrete technology parameter in blown film process is: 125 DEG C, single screw extrusion machine processing interval Zhong Yi district, 160 DEG C, 2nd district, 155 DEG C, 3rd district, 157 DEG C of flanges, 155 DEG C of transmodulators, 155 DEG C of die bodys, 160 DEG C, die head lip, 30 revs/min of single screw speeds, 3 DEG C of pipe cooling temperatures, 12 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 0.8; Second stage traction is inflation traction, and axial stretch ratio is 2.5, and stretch ratio is radially 2.0; Third stage traction is axial tension, and stretch ratio is 1.0; Fourth stage traction is axial tension, and stretch ratio is 1.3.
Embodiment 3:
Step (1). by the di(2-ethylhexyl)phosphate phenyl octyl group ester of 1kg, the hydrotalcite of 0.1kg, the sodium stearate of 0.1kg, the calcium carbonate of 0.5kg, mechanical stirring 1 hour at 50 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and methyl methacrylate of 170kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 82%, weight-average molecular weight is 120,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.5 DEG C/min; In the time that temperature rises to 60 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 90 DEG C, at the uniform velocity lower the temperature with the speed of 3 DEG C/min, be cooled to 60 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 22 DEG C slaking 8 days, obtains the modification PVDC resin of slaking;
Step (3). pass through Micro-45(ME-175-20-ZO) single screw extrusion machine carries out blowing to the modification PVDC resin of slaking, obtains pipe; Concrete technology parameter in blown film process is: 130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 165 DEG C, 2nd district, 160 DEG C, 3rd district, 160 DEG C of flanges, 160 DEG C of transmodulators, 160 DEG C of die bodys, 165 DEG C, die head lip, 50 revs/min of single screw speeds, 8 DEG C of pipe cooling temperatures, 20 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 1.1; Second stage traction is inflation traction, and axial stretch ratio is 3.5, and stretch ratio is radially 3.5; Third stage traction is axial tension, and stretch ratio is 1.1.1; Fourth stage traction is axial tension, and stretch ratio is 1.1.
Embodiment 4:
Step (1). by the silicon oxide of the Magnesium Stearate of the epoxy soybean oil of the dipropylene glycol dibenzoate of 6kg, 2.0kg, 1.0kg, 0.05kg, mechanical stirring 2 hours at 50 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and methyl acrylate of 100kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 85%, weight-average molecular weight is 130,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.2 DEG C/min; In the time that temperature rises to 55 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 85 DEG C, at the uniform velocity lower the temperature with the speed of 2.4 DEG C/min, be cooled to 55 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 25 DEG C slaking 7 days, obtains the modification PVDC resin of slaking;
Step (3). pass through Micro-45(ME-175-20-ZO) single screw extrusion machine carries out blowing to the modification PVDC resin of slaking, obtains pipe; Concrete technology parameter in blown film process is: 130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 165 DEG C, 2nd district, 164 DEG C, 3rd district, 160 DEG C of flanges, 160 DEG C of transmodulators, 160 DEG C of die bodys, 165 DEG C, die head lip, 30 revs/min of single screw speeds, 7 DEG C of pipe cooling temperatures, 18 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 1.2; Second stage traction is inflation traction, and axial stretch ratio is 2.5, and stretch ratio is radially 2.5; Third stage traction is axial tension, and stretch ratio is 1.1.3; Fourth stage traction is axial tension, and stretch ratio is 1.1.
Embodiment 5:
Step (1). by poly-(1,3 butyleneglycol/1,2 propylene glycol) adipic acid ester of 3.0kg, the epoxy oleum lini of 2.0kg, the Zinic stearas of 0.5kg, the polynite of 0.5kg, mechanical stirring 6 hours at 45 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and butyl methacrylate of 100kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 90%, weight-average molecular weight is 140,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 0.8 DEG C/min; In the time that temperature rises to 45 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 75 DEG C, at the uniform velocity lower the temperature with the speed of 1.5 DEG C/min, be cooled to 45 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 28 DEG C slaking 6 days, obtains the modification PVDC resin of slaking;
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 122 DEG C, single screw extrusion machine processing interval Zhong Yi district, 158 DEG C, 2nd district, 158 DEG C, 3rd district, 158 DEG C of flanges, 158 DEG C of transmodulators, 158 DEG C of die bodys, 162 DEG C, die head lip, 45 revs/min of single screw speeds, 6 DEG C of pipe cooling temperatures, 15 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 0.9; Second stage traction is inflation traction, and axial stretch ratio is 3.0, and stretch ratio is radially 5.0; Third stage traction is axial tension, and stretch ratio is 1.1.0; Fourth stage traction is axial tension, and stretch ratio is 1.1.
Embodiment 6:
Step (1). by the stearate of the epoxy oleum lini of the epoxy soybean oil of the polyphosphoric acid trichloro ethyl ester of 1.0kg, 1.5kg, 1.5kg, 0.5kg, the kaolin of 0.5kg, mechanical stirring 5 hours at 42 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and fumaric acid of 250kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 95%, weight-average molecular weight is 150,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 0.5 DEG C/min; In the time that temperature rises to 40 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 70 DEG C, at the uniform velocity lower the temperature with the speed of 1 DEG C/min, be cooled to 40 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 20 DEG C slaking 9 days, obtains the modification PVDC resin of slaking;
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 155 DEG C, 2nd district, 155 DEG C, 3rd district, 155 DEG C of flanges, 150 DEG C of transmodulators, 150 DEG C of die bodys, 155 DEG C, die head lip, 50 revs/min of single screw speeds, 5 DEG C of pipe cooling temperatures, 16 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 0.8; Second stage traction is inflation traction, and axial stretch ratio is 4.0, and stretch ratio is radially 5.0; Third stage traction is axial tension, and stretch ratio is 1.1.0; Fourth stage traction is axial tension, and stretch ratio is 1.4.
Embodiment 7:
Step (1). by two (2-ethyls of 6.0kg, hexyl) different titanic acid ester, the antimony thiolate of 1.0kg, the sodium stearate of 0.5kg, the Magnesium Stearate of 0.5kg, the kaolin of 0.05kg, mechanical stirring 15 hours at 38 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and maleic anhydride of 160kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 80%, weight-average molecular weight is 160,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.5 DEG C/min; In the time that temperature rises to 55 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 85 DEG C, at the uniform velocity lower the temperature with the speed of 2.5 DEG C/min, be cooled to 55 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 30 DEG C slaking 6 days, obtains the modification PVDC resin of slaking;
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 121 DEG C, single screw extrusion machine processing interval Zhong Yi district, 158 DEG C, 2nd district, 158 DEG C, 3rd district, 158 DEG C of flanges, 155 DEG C of transmodulators, 155 DEG C of die bodys, 158 DEG C, die head lip, 20 revs/min of single screw speeds, 3 DEG C of pipe cooling temperatures, 12 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 1.1; Second stage traction is inflation traction, and axial stretch ratio is 3.0, and stretch ratio is radially 3.0; Third stage traction is axial tension, and stretch ratio is 1.1.3; Fourth stage traction is axial tension, and stretch ratio is 1.2.
Embodiment 8:
Step (1). by the silicon oxide of the titanium oxide of the Zinic stearas of the Bis(lauroyloxy)dioctyltin of the dibutyl maleate of 2.0kg, 1.5kg, 1.0kg, 0.25kg, 0.25kg, mechanical stirring 10 hours at 45 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and glycidyl methacrylate of 100kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 85%, weight-average molecular weight is 170,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.0 DEG C/min; In the time that temperature rises to 55 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 85 DEG C, at the uniform velocity lower the temperature with the speed of 2.0 DEG C/min, be cooled to 55 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 23 DEG C slaking 8 days, obtains the modification PVDC resin of slaking;
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 155 DEG C, 2nd district, 155 DEG C, 3rd district, 155 DEG C of flanges, 150 DEG C of transmodulators, 150 DEG C of die bodys, 155 DEG C, die head lip, 50 revs/min of single screw speeds, 5 DEG C of pipe cooling temperatures, 16 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 0.8; Second stage traction is inflation traction, and axial stretch ratio is 2.5, and stretch ratio is radially 2.0; Third stage traction is axial tension, and stretch ratio is 1.1.0; Fourth stage traction is axial tension, and stretch ratio is 1.4.
Embodiment 9:
Step (1). by the kaolin of the polynite of the Zinic stearas of the calcium stearate of the Bis(lauroyloxy)dioctyltin of the Uniflex DBS of 1.0kg, 1.5kg, 1.0kg, 1.0kg, 0.05kg, 0.05kg, mechanical stirring 18 hours at 35 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and methacrylic acid macrogol ester of 115kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 90%, weight-average molecular weight is 180,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.3 DEG C/min; In the time that temperature rises to 55 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 85 DEG C, at the uniform velocity lower the temperature with the speed of 2.5 DEG C/min, be cooled to 55 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 28 DEG C slaking 5 days, obtains the modification PVDC resin of slaking;
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 121 DEG C, single screw extrusion machine processing interval Zhong Yi district, 158 DEG C, 2nd district, 158 DEG C, 3rd district, 158 DEG C of flanges, 155 DEG C of transmodulators, 155 DEG C of die bodys, 158 DEG C, die head lip, 20 revs/min of single screw speeds, 3 DEG C of pipe cooling temperatures, 12 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 1.1; Second stage traction is inflation traction, and axial stretch ratio is 3.0, and stretch ratio is radially 3.0; Third stage traction is axial tension, and stretch ratio is 1.1.3; Fourth stage traction is axial tension, and stretch ratio is 1.2.
Embodiment 10:
Step (1). by the calcium carbonate of the calcium stearate of the hydrotalcite of the dioctyl sebacate of 1.0kg, 3.0kg, 0.1kg, 0.1kg, mechanical stirring 20 hours at 35 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and vinylchlorid of 140kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 78%, weight-average molecular weight is 110,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 0.6 DEG C/min; In the time that temperature rises to 42 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 75 DEG C, at the uniform velocity lower the temperature with the speed of 1.0 DEG C/min, be cooled to 42 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 30 DEG C slaking 5 days, obtains the modification PVDC resin of slaking;
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 122 DEG C, single screw extrusion machine processing interval Zhong Yi district, 158 DEG C, 2nd district, 158 DEG C, 3rd district, 158 DEG C of flanges, 158 DEG C of transmodulators, 158 DEG C of die bodys, 162 DEG C, die head lip, 45 revs/min of single screw speeds, 6 DEG C of pipe cooling temperatures, 15 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 0.9; Second stage traction is inflation traction, and axial stretch ratio is 3.0, and stretch ratio is radially 5.0; Third stage traction is axial tension, and stretch ratio is 1.1.0; Fourth stage traction is axial tension, and stretch ratio is 1.1.
Embodiment 11:
Step (1). by the talcum powder of the Magnesium Stearate of the antimony thiolate of the Octyl adipate of 3.0kg, 0.5kg, 0.5kg, 0.05kg, mechanical stirring 20 hours at 35 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and vinyl cyanide of 140kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 93%, weight-average molecular weight is 120,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 0.5 DEG C/min; In the time that temperature rises to 40 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 70 DEG C, at the uniform velocity lower the temperature with the speed of 1 DEG C/min, be cooled to 40 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 20 DEG C slaking 10 days, obtains the modification PVDC resin of slaking;
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 125 DEG C, single screw extrusion machine processing interval Zhong Yi district, 160 DEG C, 2nd district, 155 DEG C, 3rd district, 157 DEG C of flanges, 155 DEG C of transmodulators, 155 DEG C of die bodys, 160 DEG C, die head lip, 30 revs/min of single screw speeds, 3 DEG C of pipe cooling temperatures, 12 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 0.8; Second stage traction is inflation traction, and axial stretch ratio is 2.5, and stretch ratio is radially 2.0; Third stage traction is axial tension, and stretch ratio is 1.0; Fourth stage traction is axial tension, and stretch ratio is 1.3.
Embodiment 12:
Step (1). by the silicon oxide of the calcium stearate of the epoxy soybean oil of the tributyl citrate of 3.0kg, 1.0kg, 0.8kg, 0.2kg, mechanical stirring 20 hours at 35 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and vinyl cyanide of 250kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 95%, weight-average molecular weight is 130,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.0 DEG C/min; In the time that temperature rises to 55 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 85 DEG C, at the uniform velocity lower the temperature with the speed of 2.0 DEG C/min, be cooled to 55 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 23 DEG C slaking 8 days, obtains the modification PVDC resin of slaking;
Step (3). by single screw extrusion machine, the modification PVDC resin of slaking is carried out to blowing, obtain pipe; Concrete technology parameter in blown film process is: 130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 155 DEG C, 2nd district, 155 DEG C, 3rd district, 155 DEG C of flanges, 150 DEG C of transmodulators, 150 DEG C of die bodys, 155 DEG C, die head lip, 50 revs/min of single screw speeds, 5 DEG C of pipe cooling temperatures, 16 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 0.8; Second stage traction is inflation traction, and axial stretch ratio is 2.5, and stretch ratio is radially 2.0; Third stage traction is axial tension, and stretch ratio is 1.1.0; Fourth stage traction is axial tension, and stretch ratio is 1.4.
Embodiment 13:
Step (1). by the stearate of the epoxy oleum lini of the Tributyl O-acetylcitrate of 3.0kg, 1.0kg, 0.8kg, the titanium oxide of 0.2kg, mechanical stirring 10 hours at 45 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and vinyl cyanide of 50kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 85%, weight-average molecular weight is 140,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.5 DEG C/min; In the time that temperature rises to 60 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 90 DEG C, at the uniform velocity lower the temperature with the speed of 3 DEG C/min, be cooled to 60 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 22 DEG C slaking 8 days, obtains the modification PVDC resin of slaking;
Step (3). pass through Micro-45(ME-175-20-ZO) single screw extrusion machine carries out blowing to the modification PVDC resin of slaking, obtains pipe; Concrete technology parameter in blown film process is: 130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 165 DEG C, 2nd district, 160 DEG C, 3rd district, 160 DEG C of flanges, 160 DEG C of transmodulators, 160 DEG C of die bodys, 165 DEG C, die head lip, 50 revs/min of single screw speeds, 8 DEG C of pipe cooling temperatures, 20 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 1.1; Second stage traction is inflation traction, and axial stretch ratio is 3.5, and stretch ratio is radially 3.5; Third stage traction is axial tension, and stretch ratio is 1.1.1; Fourth stage traction is axial tension, and stretch ratio is 1.1.
Embodiment 14:
Step (1). by the stearate of the epoxy oleum lini of the dioctyl sebacate of the Uniflex DBS of 3.0kg, 3.0kg, 1.0kg, 0.8kg, the titanium oxide of 0.2kg, mechanical stirring 15 hours at 40 DEG C, the auxiliary agent that obtains mixing;
Step (2). by the PVDC resin (multipolymer of vinylidene chloride and methyl methacrylate of 200kg, wherein the mass content of vinylidene chloride segment in PVDC resin is 80%, weight-average molecular weight is 150,000) join in ribbon stirrer, open mixing machine, and at the uniform velocity heat up with the speed of 1.2 DEG C/min; In the time that temperature rises to 55 DEG C, auxiliary agent is joined in ribbon stirrer; Continue to stir and be warming up to after 85 DEG C, at the uniform velocity lower the temperature with the speed of 2.4 DEG C/min, be cooled to 55 DEG C after discharging, to go out material be modification PVDC resin in institute; Modification PVDC resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 25 DEG C slaking 7 days, obtains the modification PVDC resin of slaking;
Step (3). pass through Micro-45(ME-175-20-ZO) single screw extrusion machine carries out blowing to the modification PVDC resin of slaking, obtains pipe; Concrete technology parameter in blown film process is: 130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 165 DEG C, 2nd district, 164 DEG C, 3rd district, 160 DEG C of flanges, 160 DEG C of transmodulators, 160 DEG C of die bodys, 165 DEG C, die head lip, 30 revs/min of single screw speeds, 7 DEG C of pipe cooling temperatures, 18 DEG C of pipe preheating temperatures, after pipe preheating, after level Four traction, form PVDC film, wherein: first step traction is axial tension, and stretch ratio is 1.2; Second stage traction is inflation traction, and axial stretch ratio is 2.5, and stretch ratio is radially 2.5; Third stage traction is axial tension, and stretch ratio is 1.1.3; Fourth stage traction is axial tension, and stretch ratio is 1.1.
Claims (6)
1. a manufacture method of eliminating the PVDC film of brilliant point, raising obstruct, is characterized in that the concrete steps of the method are:
Step (1) is the softening agent of 1.0～6.0 parts, the thermo-stabilizer of 0.1～3.0 part, the lubricant of 0.1～1.0 part, the substance A of 0.05～0.5 part by parts by weight, mechanical stirring 1～24 hour at 35～50 DEG C, the auxiliary agent that obtains mixing;
Described softening agent is cyclohexane dicarboxylic acid diisononyl esters, epoxy resin ON828, di(2-ethylhexyl)phosphate phenyl octyl group ester, dipropylene glycol dibenzoate, poly-1, one or any several mixture in 3-butyleneglycol adipic acid ester or poly-1,2-PD adipic acid ester, Trichloroethyl Phosphate, two (2-ethylhexyl) different titanic acid ester, dibutyl maleate, Uniflex DBS, dioctyl sebacate, Octyl adipate, tributyl citrate, Tributyl O-acetylcitrate;
Described thermo-stabilizer is the one or any several mixture in antimony thiolate, Bis(lauroyloxy)dioctyltin, hydrotalcite, epoxy soybean oil, epoxy oleum lini;
Described lubricant is the one or any several mixture in stearate, calcium stearate, sodium stearate, Magnesium Stearate, Zinic stearas;
Described substance A is the one or any several mixture in talcum powder, calcium carbonate, titanium oxide, silicon oxide, polynite, kaolin;
Step (2) joins polyvinylidene chloride resin in ribbon stirrer, opens mixing machine, and at the uniform velocity heats up; In the time that temperature rises to 40～60 DEG C, auxiliary agent is joined in ribbon stirrer, the weight that adds auxiliary agent is 1.0～10.0% of polyvinylidene chloride resin weight; Continue to stir and be warming up to after 70～90 DEG C, start at the uniform velocity cooling, be cooled to 40～60 DEG C after discharging, to go out material be modified polyvinilidene vinyl chloride resin in institute; Modified polyvinilidene vinyl chloride resin is naturally cooled to normal temperature, and pack is placed in the isoperibol of 20～30 DEG C slaking 5～10 days, obtains the modification PVDC resin of slaking;
The weight-average molecular weight of described polyvinylidene chloride resin is 10～180,000, for one of them multipolymer of vinylidene chloride and vinylchlorid, vinyl cyanide, methyl methacrylate, methyl acrylate, butyl methacrylate, fumaric acid, maleic anhydride, glycidyl methacrylate, methacrylic acid macrogol ester, wherein the mass content of vinylidene chloride segment in PVDC resin is 75～95%;
Step (3) is carried out blowing by single screw extrusion machine to the modification PVDC resin of slaking, obtains pipe; 2～8 DEG C of pipe cooling temperatures, 10～20 DEG C of pipe preheating temperatures form polyvinylidene chloride film after pipe preheating after level Four traction.
2. a kind of manufacture method of eliminating brilliant point, improving the PVDC film intercepting as claimed in claim 1, is characterized in that: the weight that adds auxiliary agent in step (2) is 2.0～6.0% of polyvinylidene chloride resin weight.
3. a kind of manufacture method of eliminating brilliant point, improving the PVDC film intercepting as claimed in claim 1, is characterized in that: the speed at the uniform velocity heating up in step (2) is 0.5～1.5 DEG C/min, and at the uniform velocity the speed of cooling is 1～3 DEG C/min.
4. a kind of manufacture method of eliminating brilliant point, improving the PVDC film intercepting as claimed in claim 1, it is characterized in that: the weight-average molecular weight of described polyvinylidene chloride resin is 11～150,000, for one of them multipolymer of vinylidene chloride and vinylchlorid, vinyl cyanide, methyl methacrylate, the mass content of vinylidene chloride segment in PVDC resin is 80～90%.
5. a kind of manufacture method of eliminating brilliant point, improving the PVDC film intercepting as claimed in claim 1, it is characterized in that in step (3), the concrete technology parameter in blown film process is: 120～130 DEG C, single screw extrusion machine processing interval Zhong Yi district, 155～165 DEG C, 2nd district, 150～164 DEG C, 3rd district, 155～160 DEG C of flanges, 150～160 DEG C of transmodulators, 150～160 DEG C of die bodys, 155～165 DEG C, die head lip, 20～50 revs/min of single screw speeds.
6. as claimed in claim 1ly a kind ofly eliminate brilliant point, improve the manufacture method of PVDC film intercepting, it is characterized in that the level Four described in step (3) draw specifically: first step traction is axial tension, and stretch ratio is 0.8～1.2; Second stage traction is inflation traction, and axial stretch ratio is 2.5～4.0, and stretch ratio is radially 2.0～5.0; Third stage traction is axial tension, and stretch ratio is 1.0～1.3; Fourth stage traction is axial tension, and stretch ratio is 1.1～1.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110347831.2A CN102443231B (en) | 2011-11-07 | 2011-11-07 | Manufacturing method of PVDC film with crystal point eliminated and barrier property improved |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110347831.2A CN102443231B (en) | 2011-11-07 | 2011-11-07 | Manufacturing method of PVDC film with crystal point eliminated and barrier property improved |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102443231A CN102443231A (en) | 2012-05-09 |
| CN102443231B true CN102443231B (en) | 2014-07-02 |
Family
ID=46006189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110347831.2A Active CN102443231B (en) | 2011-11-07 | 2011-11-07 | Manufacturing method of PVDC film with crystal point eliminated and barrier property improved |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102443231B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI567125B (en) * | 2014-02-18 | 2017-01-21 | Kureha Corp | Plastic wrap |
| CN104385565A (en) * | 2014-09-03 | 2015-03-04 | 福建师范大学 | Preparation method for three-layer co-extruded composite high barrier blown film |
| CN105599262A (en) * | 2016-01-21 | 2016-05-25 | 长乐长宏工贸有限公司 | Method for prolonging service life of extruder and method for producing polymer melt |
| CN106832689A (en) * | 2016-11-30 | 2017-06-13 | 四川旭华制药有限公司 | A kind of preparation method of acceptable packaging material |
| CN106633538A (en) * | 2016-11-30 | 2017-05-10 | 四川旭华制药有限公司 | Preparation method of drug packaging material |
| CN110511515A (en) * | 2018-05-21 | 2019-11-29 | 郑州新生印务有限公司 | A kind of high-barrier PVDC preservative film |
| CN108773140B (en) * | 2018-06-05 | 2024-04-05 | 洛阳兴瑞新型膜材料有限公司 | Nano modified high-barrier composite film and production method thereof |
| CN109111659A (en) * | 2018-08-02 | 2019-01-01 | 洛阳兴瑞新材料科技有限公司 | A kind of super thick PVDC film and its manufacturing method |
| CN109206797B (en) * | 2018-08-30 | 2021-01-29 | 佛山晨华新材料有限公司 | Preservative film based on vinylidene chloride-ethylene-acrylonitrile copolymer and preparation method thereof |
| CN110467787A (en) * | 2019-09-05 | 2019-11-19 | 安徽省聚科石墨烯科技股份公司 | A kind of high barrier graphene modified plastics |
| CN111410804A (en) * | 2020-03-04 | 2020-07-14 | 华南理工大学 | High-barrier vinylidene chloride-methyl acrylate copolymer resin film and manufacturing method thereof |
| CN114044995A (en) * | 2021-12-01 | 2022-02-15 | 郑州新生印务有限公司 | PVDC high-barrier substrate film and preparation method thereof |
| CN114987017B (en) * | 2022-04-19 | 2023-10-10 | 毕玛时软包装（苏州）有限公司 | Low-migration high-barrier flexible packaging film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4686148A (en) * | 1985-07-15 | 1987-08-11 | W. R. Grace & Co., Cryovac Div. | Vinylidene chloride composition and film made therefrom |
| CN1183111A (en) * | 1995-04-27 | 1998-05-27 | 吴羽化学工业株式会社 | Vinylidene chloride copolymer resin composition, film produced therfrom, extrusion process for the composition, and process for producing the film |
| CN1215739A (en) * | 1993-03-05 | 1999-05-05 | 旭化成工业株式会社 | Vinylidene chloride copolymer composition contg. monolayer film |
-
2011
- 2011-11-07 CN CN201110347831.2A patent/CN102443231B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4686148A (en) * | 1985-07-15 | 1987-08-11 | W. R. Grace & Co., Cryovac Div. | Vinylidene chloride composition and film made therefrom |
| CN1215739A (en) * | 1993-03-05 | 1999-05-05 | 旭化成工业株式会社 | Vinylidene chloride copolymer composition contg. monolayer film |
| CN1183111A (en) * | 1995-04-27 | 1998-05-27 | 吴羽化学工业株式会社 | Vinylidene chloride copolymer resin composition, film produced therfrom, extrusion process for the composition, and process for producing the film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102443231A (en) | 2012-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102443231B (en) | Manufacturing method of PVDC film with crystal point eliminated and barrier property improved | |
| CN105175963B (en) | Chlorinated polyvinyl chloride modified material | |
| CN101397375B (en) | PVC low foaming wood-plastic decorating material and production method thereof | |
| CN108659421B (en) | Chlorinated polyvinyl chloride composition and pipe preparation method | |
| CN103224674A (en) | Polyvinyl chloride modifier, polyvinyl chloride composition and preparation method of polyvinyl chloride composition | |
| CN102549070A (en) | Method for manufacturing a polyester composition having improved impact properties | |
| WO2011079492A1 (en) | Fully biodegradable multi-component film material and preparing method thereof | |
| WO2023221849A1 (en) | Acid nucleating agent for polyhydroxyalkanoate and polyhydroxyalkanoate molded article | |
| CN112679645B (en) | Preparation method of high-fluidity modified polychlorotrifluoroethylene resin | |
| WO2024060635A1 (en) | Polyhydroxyalkanoate composition containing hydroxy acid nucleating agent, polyhydroxyalkanoate molded body, and preparation method therefor | |
| CN102206406B (en) | Method for preparing transparent heat-resistance polylactic acid modification material | |
| CN109880265A (en) | A kind of CPVC blending preparation method for material of high thermal stability | |
| CN106832698A (en) | A kind of chlorinated polyvinyl chloride tubes composition and tubing preparation method | |
| CN104086942A (en) | Special material composition with low metal cohesiveness for automobile tail fins | |
| CN103601836A (en) | Copolymer used as polyvinyl chloride multifunctional processing modifier and synthetic method thereof | |
| JPS6215243A (en) | Production of molded article | |
| CN101580563A (en) | Preparation method of PVDC composition by VDC/MA copolymerization | |
| CN112552618B (en) | High-fluidity hard PVC material for injection molding and preparation method thereof | |
| CN115772305A (en) | Preparation method of CPVC cold and hot water pipe | |
| JP2019038996A (en) | Hard polyvinyl chloride molding and method for producing the same | |
| CN103450607A (en) | Preparation method of thermostable polyvinylidene fluoride (PVDF) resin | |
| JPH01308439A (en) | Production of molding | |
| KR101218406B1 (en) | Synthetic resin composition and manufacturing the same | |
| CN112194869A (en) | Special PVA material capable of being thermoplastically processed and preparation method thereof | |
| CN110746720B (en) | Production method of high-performance PVC-O pipe |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xue Lixin Inventor after: Guo Zhiyi Inventor after: Liu Fu Inventor after: Han Jinming Inventor after: Wang Yi Inventor after: Du Jili Inventor after: Zhu Qiliang Inventor after: Chen Linyan Inventor before: Xue Lixin Inventor before: Liu Fu Inventor before: Wang Yi Inventor before: Zhu Qiliang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: XUE LIXIN LIU FU WANG YI ZHU QILIANG TO: XUE LIXIN GUO ZHIYI LIU FU HAN JINMING WANG YI DU JILI ZHU QILIANG CHEN LINYAN |
|
| ASS | Succession or assignment of patent right |
Owner name: NINGBO JUHUA CHEMICAL + SCIENCE CO., LTD. Effective date: 20121026 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20121026 Address after: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Applicant after: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien Applicant after: Ningbo Juhua Chemical Industry Technology Co., Ltd. Address before: No. 519 Road, 315201 Zhejiang Zhuang Zhenhai District of city of Ningbo Province Applicant before: Ningbo Institute of Material Technology and Engineering Chinese Academy of Scien |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |